Thickened lubricating oil



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UNITED STATES PATENT OFFICE THIOKENED LUBRICATING OIL Per 1:. Frolich, Roselle, N. 1., escignor to stand ard-Oil Development Company, a corpora on V of Delaware .No Drawing. Application October 21, 19:3, Serial No. 694,616

5 Claims. (01. 196-151) 'Ihis invention relates to improved lubricating from unsaturated hydrocarbons. Many such compositions comprising" solutions of synthetic products are insoluble in practically all solvents resinous bodies in lubricating oils and relates and are obviously unsuited for the present in- ,more particularly to the improvement of the ventlon. The polymerization and condensation 5 viscosity and viscosity indexof inferior quality products intended for use in this invention are- 5 lubricating oils by addition thereto of resins prethose resins and resinous products of relatively pared by polymerization and/or condensation high molecular weight, say above 800 to 1000, of oleilnes and dioleflnes or mixtures thereof such and including the range to 2,000, 5,000, 10,000 as are found in cracked naphthas. and even higher. which are soluble in benzol, and

A class of hydrocarbon resins of varying meltwhich preferably are brittle and readily friable 10 r in: point, friability and color, and which are solids which'become. plastic on heating. Such soluble in benzol and gasoline and are insoluble products are designated. by th'e term resin as in ethyl alcohol and acetone is obtained by the used in the claims.

polymerization -and condensation of cracked It is recognized that the presence of a relative naphthas or of the unsaturated components ly smaller proportion of impurities, such as heavy 15 thereof by the application of heat and pressure oils, which may have been present in the initial or by action of suitable polymerizing agents such materials or may be formed during the polymeras the active halides, for example aluminum chlo-- ization and condensation reaction, may so affect ride, zinc chloride, boron fluoride, and the like. t e p ys c p pe es of the crude product t a go It has now been found that these resins are soluit may be semi-solid, tacky, so toughened as not ble in lubricating oils; particularly those derived to be brittle or pulveriz lil or otherwise modifrom asphaltic or naphthenic base crudes, and lied. The crude prod tai e resin that the resulting solutions have a materially may also be us d f t pu p s f th s nv nhigher viscosity and viscosity index than the tion, provided the impurities are not present in ori inal lubricating oil. ,It is an object of this sumcieht' quantities to offset the advantageous g5 invention to increase the viscosity and to imeffect of the resin. However. it'is en r l y p .prove the lubricating and other qualities of such erable to use resins that are sufliciently pure to inferior lubricating oils by addition thereto of be brittle and pulverizable solids at room temsuch resins. perature. The resin may be purified by distll1a- 3o Resins suitable for this invention may be pretion of vaporlzable oils, preferably in high vaco pared in a great varietyof ways; for example relm and may b separated f Oils and atively pure oleilnes or mixtures of oleiines and ph l ma y u b Selective Solvents, Such diolefines, such as amylene and isoprene, may as uefied hydrocarbon e pet ether. be condensed to resins by addition of aluminum nap thas. a mixture f be and a tone. and

chloride or other suitable halide polymerizing, the like. 35

agent, as described in German Patent 278,4;86 to Th a ov resins may be us d t thi ken and Schering. Cracked naphthas such as the to improve the viscosity index and other lubridensates or oil gas drips boiling below 200 1 eating characteristics of lubricating oils. This obtained in the gasiiication of gas oil may ,be is illustrated in the following examples:

40 treatedwithasmallamountofalmninumchlwride as described in U. S. Patent 811,563'to Ihart. .The mixture is filtered and a resin ob- A petroleum naphtha obtained by cracking gas tained from the filtrate as a residue by distillaoil in vapor phase, 'at high temperature and lbw tion or evaporation oi volatile constituents. As pressure, is carefullyfractionated bydistlllation.

another example a resin may be prepared by The fraction boiling below about-180 C. is agi- 45 contacting a cracked naphtha boiling from 60 to tated with about 20% by weight of anhydrous 15.0 C. with zinc chloride as described aluminum chloride which is added in smallquanin British Patent 3572 of 1914. By still another titles during continuous and vigorous agitation method the liquid fraction obta ned in crackin and cooling to'maintain the reagents at about sam le 1 9 5o petroleum oil in vapor phase at 650 C. may be room temperature and preferably below about polymerized to a hard resin by the application 40 0., as described by Thomas and Carmody, of heat without a catalyst as described in U. 8. J. Ind. 8: Eng. Chem. 24 (1932) p. 1125, and in 1,703,950. U. 8. Patent 1,836,629. The reaction mixture is Itisrecognized that many types of polymerlzathen hydrolyzed. the sludge withdrawn and the tlon and condensation products can be obtained resin obtained as a residue on distillationof the so Seconds at 100 F 360 543 Seconds at 210 F 50 58.5 Viscosity index. 38 55 EmampleZ A fraction boiling in the gasoline range, containing olefin and diolefln, and probably aromatic and substituted aromatic hydrocarbons, and produced by vapor phase cracking of a petroleum gas oil fraction at high temperatures and low pressures by the Gyro process, is cooled to 70" F.

Boron fluoride is bubbled through this fraction for about one hour, with addition of carbon dioxide snow to maintain the temperature continuously at about '70 F. (It is desirable when usingboron fluoride to work at low temperatures, such as F. to 90 F.) A noticeable thickening of the mixture occurs. allowed to warm up to room temperature. Any boron fluoride present is hydrolyzed, and the gasoline hydrocarbons are removed by distillation. There is thus obtained a residue consisting ofabout equal portions of a resin and an oil, the total residue corresponding to 30% of the original gasoline. The oil is removed by distillation under a vacuum of about mm. of mercury to a temperature of about 450 F., the resin being obtained as the residue. A blend of this resin in the Coastal oil described in Example 1 gives the following inspection:

Saybolt viscosity:

Seconds at 100 F 655 Seconds at 210 F 62.2 V. I 52 Similar blends may be prepared with resins prepared by other methods as described above and with other types of lubricating oils. It has been found that these resins are soluble only with diiiiculty in high grade lubricating oils such as those of the Pennsylvania type. is accordingly particularly suited for the improve: ment of inferior quality lubricating oils such as lubricating oils having a viscosity index from about 50 to 0, or lower. Such lubricating oils are obtained from asphaltic, naphthem'c and aromatic base crudes such as Coastal and California, and may also be obtained from othermineral carbonaceous materials, as by the liquefaction or destructive distillation of coal, shale, and the like. Similar hydrocarbon oils may be prepared synthetically or by polymerization and condensation of lower molecular weight hydrocarbons. Of I course, with resins of suitable solubility, blends of exceptionally high viscosity index may be prepared with high grade Pennsylvania type oils. The amount of the resin used in any particular The mixture is then This invention lubricating composition will depend upon the solubility of the resin in the oil used and on the extent of improvement desired. Generally, with oils having a viscosity index of 0 to 50, improved lubricants are prepared with about 2 to 10% of the resin in the composition, although lower or higher concentrations such as or 1% to or 25% or moremay be used, and will be found suitable with oils of unusually high or low viscosity and viscosity index.

The color, purity, solubility in petroleum solvents, and other qualities of these resins may be modifled" or improved by various methods, and the improved resins may also be used to prepare blends with lubricating oils as described above.

The resins may be purified and improved by suitsulfurized oils, dyes and the like as will be understood.

This inventlon is not to be limited to any specific examples which have been presented herein solely for purpose of illustration, but only by the following claims in which it is desired to claim all novelty insofar as the prior art permits.

I claim:

1. Lubricant comprising a mineral oil and a normally solid thickener produced by the condensation of olefin and diolefin hydrocarbons.

2. Lubricant comprising a mineral oil and a normally solid thickener produced by the condensation of olefin and diolefln hydrocarbons in the presence of boron fluoride at a low tempera ture.

3. Method for improving the lubricating characteristics oflubricating oils of petroleum origin having a viscosity index below 50, which comprises dissolving therein about to 25% of a resin prepared by treating a cracked naphtha with an active halide polymerizing agent under conditions adapted to produce condensation products of olefine and di-olefine hydrocarbons present in said cracked naphtha. I

4.'Method according to claim 3 in which the cracked naphtha boils below 180 C.

5. Method according to claim 3 in which the resin is prepared by treating a cracked naphtha boiling below 180 C. with anhydrous aluminum chloride at a temperature below about 40 C. and separating the resin from the resulting mixture.

PER K. EROLICH. 

